[geo] Re: Nickel nanoparticles catalyse reversible hydration of carbon dioxide for mineralization carbon capture and storage OR Sea Urchins May Save the World

[David Lewis]

I was interested that Siller and Bhaduri, authors of this nickel 
nanoparticle paper, compared what they think nickel nanoparticles can do *
favorably* to what carbonic anhydrase can do.

A discussion of the properties and significance of carbonic anhydrase is 
located on the Stanford website, i.e. at the Global Climate and Energy 
Project, i.e. in this Jennifer Wilcox Carbon Capture 101 
Tutorial. 
   

Wilcox devotes most of the tutorial discussing the best CO2 capture 
chemistry presently commercially available, i.e. amine chemistry. * *

As an aside, she brought up carbonic anhydrase at minute 34:30.  A 
transcript:  

"There is a special case called carbonic anhydrase.  This is an enzyme. 
 This is how we filter out CO2 in our own bodies.  So this is present in 
the red blood cells of mammals.  And essentially carbonic anhydrase is a 
zinc  based enzyme and you can see here there are three histadine groups 
surrounding the zinc.  And you have water associated with it.  In solution, 
the proton will go into solution and so you have this hydroxyl group 
directly bound to the zinc and so what ends up happening is that OH will 
hydrate CO2.  So [garbled] its carbonate interaction with the OH of the 
zinc, and the interesting aspect about this is that it occurs about ten 
orders of magnitude faster.  So CO2 to bicarbonate formation is up to ten 
orders of magnitude faster than CO2 in aqueous solution without anything 
added.  That's just in water.   * It can be anywhere from four to six 
orders of magnitude greater than amine chemistry - for forming carbonate 
from CO2.  So it's a pretty significant enzyme*.  Currently though the 
source is questionable, where we can get this, since it is only available 
in red blood cells.  And, you know, that's limited.  So there are a lot of 
groups - there's a group at Columbia, there's a group at Lawrence Livermore 
National Labs, working on synthetically making carbonic anhydrase as 
additives for the absorption process for separation."

I asked Siller for a description of the speed she and Bhaduri observed 
nickel could catalyse CO2 to carbonic acid, in the terms Wilcox uses, i.e. 
compared to CO2 in water, and/or compared to amine chemistry, i.e. CO2 and 
amines in water.  Her reply:

"We have tried to determine the rates of conversion of CO2 to acid by 
nickel nanoparticles with stop-flow technique to compare them with carbonic 
anhydrase from the literature - however we have problems since nobody 
before us did not work (sic) on this system and if we just copy literature 
and try to use reagents which are used for CO2 capture by carbonic 
anhydrase... the measured rates are unreliable  So we are trying to 
find the right reagents for kinetic measurements".  

I asked Klaus Lackner for his reaction about the importance of this 
discovery that nickel acts similarly to carbonic anhydrase.  He commented 
on the Siller/Bhaduri plan to remove carbonic acid as it forms so the 
nickel can continually produce more, by using olivine: 

"Keep in mind that other people have used bicarbonate brines to digest 
olivine and they were rate limited too.  These processes which start with 
bicarbonate ions in the water end up being severely rate limited even 
though they simply ignored the question of how to get the CO2 in the 
water".  

I asked Siller what she thought of what Lackner brought up.  Siller:  "we 
have some ideas we are exploring currently".  

Lackner also thought having a magnetic catalyst wasn't necessarily going to 
be a game changer.  "With regard to the ability to recover the catalyst. 
 Yes it is easy to pick up nickel magnetically, but the same will happen to 
the iron that one invariably finds in the olivine rock.  So magnetic 
separation will leave you with an ever larger pile of magnetite".  

Siller:  "if we do nickel separation before (have two tank process) we 
would not need to worry about the iron".

Lackner:  "I am not entirely convinced that carbonic anhydrase could not 
become similarly cheap, nor am I convinced that getting CO2 into the water 
is   therate limiting step".

Siller:  "regarding the cheap carbonic anhydrase - this would be great 
 [however] it should be reusable and not easily degradable (this would be 
probably harder to achieve when compared to inorganic catalysts such as 
nickel nanoparticles).  For nickel nanoparticles, process is easily 
scalable - you can buy machine on the market now which will make Ni 
nanoparticles."

Siller:  "conversion of CO2 to acid if you go through the chemistry 
literature is*   a*rate limited process".

Lackner:  "So I would argue this discovery seems to be a good piece of 
progress.  It is a very nice tool added to the tool box, but it may take a 
lot more than that to actually solve the problem".

DOE published Basic Research Needs for Carbon Capture Beyond 
2020 
which 
starts out

RE: [geo] Re: Nickel nanoparticles catalyse reversible hydration of carbon dioxide for mineralization carbon capture and storage OR Sea Urchins May Save the World

[Rau, Greg]

Anyone have an e-copy of Siller and Bhaduri?
Still unclear how catalysts are a panacea for CO2 air capture. There still 
needs to be a chemical driving force that transfers gas into solution and keeps 
it there. Adding CA, nano particles, etc to water doesn't magically consume 
CO2. You've got to remove acid or add base to the solution to drive the 
reaction. If you are talking about mitigating point sources, then obviously 
pCO2 flue gas > pCO2 water is the driving force. Then keeping it in solution 
requires some additional chemistry like adding a base. If minerals are added as 
the base, carbonates would be must preferred over silicates because of CO2 
reaction kinetics. I can't imagine CO2 hydration being the rate limiting step 
in most silicate weathering, so unclear how a hydration catalyst helps here, 
but i should read the paper.
-Greg

From: geoengineering@googlegroups.com [geoengineering@googlegroups.com] on 
behalf of David Lewis [jrandomwin...@gmail.com]
Sent: Thursday, March 07, 2013 3:38 PM
To: geoengineering@googlegroups.com
Subject: [geo] Re: Nickel nanoparticles catalyse reversible hydration of carbon 
dioxide for mineralization carbon capture and storage OR Sea Urchins May Save 
the World

I was interested that Siller and Bhaduri, authors of this nickel nanoparticle 
paper, compared what they think nickel nanoparticles can do favorably to what 
carbonic anhydrase can do.

A discussion of the properties and significance of carbonic anhydrase is 
located on the Stanford website, i.e. at the Global Climate and Energy Project, 
i.e. in this Jennifer Wilcox Carbon Capture 101 
Tutorial<http://vimeo.com/30557085>.

Wilcox devotes most of the tutorial discussing the best CO2 capture chemistry 
presently commercially available, i.e. amine chemistry.

As an aside, she brought up carbonic anhydrase at minute 34:30.  A transcript:

"There is a special case called carbonic anhydrase.  This is an enzyme.  This 
is how we filter out CO2 in our own bodies.  So this is present in the red 
blood cells of mammals.  And essentially carbonic anhydrase is a zinc  based 
enzyme and you can see here there are three histadine groups surrounding the 
zinc.  And you have water associated with it.  In solution, the proton will go 
into solution and so you have this hydroxyl group directly bound to the zinc 
and so what ends up happening is that OH will hydrate CO2.  So [garbled] its 
carbonate interaction with the OH of the zinc, and the interesting aspect about 
this is that it occurs about ten orders of magnitude faster.  So CO2 to 
bicarbonate formation is up to ten orders of magnitude faster than CO2 in 
aqueous solution without anything added.  That's just in water.It can be 
anywhere from four to six orders of magnitude greater than amine chemistry - 
for forming carbonate from CO2.  So it's a pretty significant enzyme.  
Currently though the source is questionable, where we can get this, since it is 
only available in red blood cells.  And, you know, that's limited.  So there 
are a lot of groups - there's a group at Columbia, there's a group at Lawrence 
Livermore National Labs, working on synthetically making carbonic anhydrase as 
additives for the absorption process for separation."

I asked Siller for a description of the speed she and Bhaduri observed nickel 
could catalyse CO2 to carbonic acid, in the terms Wilcox uses, i.e. compared to 
CO2 in water, and/or compared to amine chemistry, i.e. CO2 and amines in water. 
 Her reply:

"We have tried to determine the rates of conversion of CO2 to acid by nickel 
nanoparticles with stop-flow technique to compare them with carbonic anhydrase 
from the literature - however we have problems since nobody before us did not 
work (sic) on this system and if we just copy literature and try to use 
reagents which are used for CO2 capture by carbonic anhydrase... the measured 
rates are unreliable  So we are trying to find the right reagents for 
kinetic measurements".

I asked Klaus Lackner for his reaction about the importance of this discovery 
that nickel acts similarly to carbonic anhydrase.  He commented on the 
Siller/Bhaduri plan to remove carbonic acid as it forms so the nickel can 
continually produce more, by using olivine:

"Keep in mind that other people have used bicarbonate brines to digest olivine 
and they were rate limited too.  These processes which start with bicarbonate 
ions in the water end up being severely rate limited even though they simply 
ignored the question of how to get the CO2 in the water".

I asked Siller what she thought of what Lackner brought up.  Siller:  "we have 
some ideas we are exploring currently".

Lackner also thought having a magnetic catalyst wasn't necessarily going to be 
a game changer.  "With regard to the ability to recover the catalyst.  Yes it 
is easy to pick up nickel mag

Re: [geo] Re: Nickel nanoparticles catalyse reversible hydration of carbon dioxide for mineralization carbon capture and storage OR Sea Urchins May Save the World

[David Lewis]

I have a copy I got from Dr. Siller.  She said I could send it to anyone I 
felt like.  I didn't ask for and don't have her permission to post a copy 
for public access.  Anyone wishing to see the paper, email me.  

On Sunday, March 10, 2013 9:05:17 PM UTC-7, Greg Rau wrote:
>
>  Anyone have an e-copy of Siller and Bhaduri? 
> Still unclear how catalysts are a panacea for CO2 air capture. There still 
> needs to be a chemical driving force that transfers gas into solution and 
> keeps it there. Adding CA, nano particles, etc to water doesn't magically 
> consume CO2. You've got to remove acid or add base to the solution to drive 
> the reaction. If you are talking about mitigating point sources, then 
> obviously pCO2 flue gas > pCO2 water is the driving force. Then keeping it 
> in solution requires some additional chemistry like adding a base. If 
> minerals are added as the base, carbonates would be must preferred over 
> silicates because of CO2 reaction kinetics. I can't imagine CO2 hydration 
> being the rate limiting step in most silicate weathering, so unclear how a 
> hydration catalyst helps here, but i should read the paper.
> -Greg
>  --
> *From:* geoengi...@googlegroups.com  [
> geoengi...@googlegroups.com ] on behalf of David Lewis [
> jrando...@gmail.com ]
> *Sent:* Thursday, March 07, 2013 3:38 PM
> *To:* geoengi...@googlegroups.com 
> *Subject:* [geo] Re: Nickel nanoparticles catalyse reversible hydration 
> of carbon dioxide for mineralization carbon capture and storage OR Sea 
> Urchins May Save the World
>
>   I was interested that Siller and Bhaduri, authors of this nickel 
> nanoparticle paper, compared what they think nickel nanoparticles can do *
> favorably* to what carbonic anhydrase can do.
>
>  A discussion of the properties and significance of carbonic anhydrase is 
> located on the Stanford website, i.e. at the Global Climate and Energy 
> Project, i.e. in this Jennifer Wilcox Carbon Capture 101 
> Tutorial<http://vimeo.com/30557085>. 
>
>
>  Wilcox devotes most of the tutorial discussing the best CO2 capture 
> chemistry presently commercially available, i.e. amine chemistry. * *
>
>  As an aside, she brought up carbonic anhydrase at minute 34:30.  A 
> transcript:  
>
>  "There is a special case called carbonic anhydrase.  This is an enzyme. 
>  This is how we filter out CO2 in our own bodies.  So this is present in 
> the red blood cells of mammals.  And essentially carbonic anhydrase is a 
> zinc  based enzyme and you can see here there are three histadine groups 
> surrounding the zinc.  And you have water associated with it.  In solution, 
> the proton will go into solution and so you have this hydroxyl group 
> directly bound to the zinc and so what ends up happening is that OH will 
> hydrate CO2.  So [garbled] its carbonate interaction with the OH of the 
> zinc, and the interesting aspect about this is that it occurs about ten 
> orders of magnitude faster.  So CO2 to bicarbonate formation is up to ten 
> orders of magnitude faster than CO2 in aqueous solution without anything 
> added.  That's just in water.   * It can be anywhere from four to six 
> orders of magnitude greater than amine chemistry - for forming carbonate 
> from CO2.  So it's a pretty significant enzyme*.  Currently though the 
> source is questionable, where we can get this, since it is only available 
> in red blood cells.  And, you know, that's limited.  So there are a lot of 
> groups - there's a group at Columbia, there's a group at Lawrence Livermore 
> National Labs, working on synthetically making carbonic anhydrase as 
> additives for the absorption process for separation."
>
>  I asked Siller for a description of the speed she and Bhaduri observed 
> nickel could catalyse CO2 to carbonic acid, in the terms Wilcox uses, i.e. 
> compared to CO2 in water, and/or compared to amine chemistry, i.e. CO2 and 
> amines in water.  Her reply:
>
>  "We have tried to determine the rates of conversion of CO2 to acid by 
> nickel nanoparticles with stop-flow technique to compare them with carbonic 
> anhydrase from the literature - however we have problems since nobody 
> before us did not work (sic) on this system and if we just copy literature 
> and try to use reagents which are used for CO2 capture by carbonic 
> anhydrase... the measured rates are unreliable  So we are trying to 
> find the right reagents for kinetic measurements".  
>
>  I asked Klaus Lackner for his reaction about the importance of this 
> discovery that nickel acts similarly to carbonic anhydrase.  He commented 
> on the Siller/Bhaduri plan to remove carbonic acid as it forms so the 
> n